KR20160110591A

KR20160110591A - Ecofriendly sheet and method for preparing the same

Info

Publication number: KR20160110591A
Application number: KR1020150032454A
Authority: KR
Inventors: 남승백; 손종석
Original assignee: (주)엘지하우시스
Priority date: 2015-03-09
Filing date: 2015-03-09
Publication date: 2016-09-22
Also published as: KR102006284B1

Abstract

The present invention relates to an eco-friendly sheet and a production method thereof. According to the present invention, the eco-friendly sheet includes: a base material layer; a printing layer formed on an upper part of the base material layer; and a transparent layer formed on an upper part of the printing layer. The transparent layer is produced by processing a cross-linked and modified polylactic acid (PLA) resin which ensures easy processability and increases flexibility and heat resistance of the transparent layer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an eco-

The present invention relates to an environmentally friendly sheet and a manufacturing method thereof.

Sheets made of petroleum resins such as polyvinyl chloride (PVC) are widely used in buildings such as houses, mansions, apartments, offices or shops.

Such a sheet is manufactured by extrusion or car-rendering using a resin such as polyvinyl chloride (PVC). However, since the raw materials are obtained entirely from crude oil, which is a limited resource, it is expected that problems such as difficulty in supplying raw materials in the future due to depletion of petroleum resources are expected to occur.

In addition, even considering the recent interest in environmental problems, polyvinyl chloride (PVC) -based sheets are liable to discharge harmful substances and burden the environment even when they are disposed of.

Due to these problems, recently, PLA (Poly Lactic Acid) resin extracted and synthesized from plant resources has attracted attention as a means to replace the petroleum resin.

However, the sheet made of such a PLA resin has disadvantages in that it is difficult to carry out a multilayer lamination process because it is sticky to the processing equipment during the processing of the thermal plywood or lacks viscoelasticity at high temperature processing, .

The present invention relates to a substrate layer; A printing layer formed on the base layer; And a transparent layer formed on the printed layer, wherein the transparent layer is obtained by processing a crosslinked modified PLA resin composition.

However, the technical problem to be solved by the present invention is not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

The base layer or the print layer may be a PVC resin sheet.

The crosslinked modified PLA resin composition may include a PLA resin, a thermal initiator, and a crosslinking monomer, and may be modified through a crosslinking reaction at the time of opening.

The crosslinked modified PLA resin composition may contain 0.1 to 10 parts by weight of a thermal initiator and 0.1 to 10 parts by weight of a crosslinking monomer based on 100 parts by weight of the PLA resin.

The crosslinked modified PLA resin composition may further include at least one selected from the group consisting of a nonphthalate plasticizer, a lubricant, calcium carbonate, and titanium dioxide.

The crosslinked modified PLA resin composition comprises 5 to 100 parts by weight of a nonphthalate plasticizer, 0.1 to 10 parts by weight of a lubricant, 5 to 1000 parts by weight of calcium carbonate, and 0.5 to 50 parts by weight of titanium dioxide, based on 100 parts by weight of the PLA resin , And < / RTI >

The base layer may be formed to a thickness of 0.05 to 3.0 mm.

The printing layer may be formed to a thickness of 0.1 to 0.5 mm.

The transparent layer may be obtained by processing a crosslinked modified PLA resin composition by a car rendering method.

The transparent layer may be formed to a thickness of 0.1 to 1.0 mm.

A surface treatment layer may be further formed on the transparent layer.

The surface treatment layer may be formed to a thickness of 0.01 to 0.1 mm.

An adhesive layer may be further formed on the bottom of the base layer.

In one embodiment of the present invention, there is provided a method for producing a transparent resin composition, comprising the steps of: preparing a transparent layer by processing a crosslinked modified PLA resin composition; And laminating the base layer, the print layer formed on the base layer, and the transparent layer formed on the print layer.

The laminate may be performed at a temperature of 120 to 160 캜.

The eco-friendly sheet according to the present invention includes a transparent layer obtained by processing a crosslinked modified PLA resin composition, so that the crosslinked modified PLA resin composition is easy to process, has the effect of improving the flexibility and heat resistance of the transparent layer, There is an advantage that the discharge of harmful substances is small and the disposal is easy.

In addition, the environmentally friendly sheet according to the present invention can be manufactured in a flat shape by preventing the curing by laminating a PVC resin sheet and a transparent layer obtained by processing a crosslinked modified PLA resin composition.

1 is a schematic cross-sectional view of an environmentally friendly sheet according to an embodiment of the present invention.
2 is a schematic cross-sectional view of an environmentally friendly sheet according to another embodiment of the present invention.

DISCLOSURE OF THE INVENTION The inventors of the present invention have completed the present invention by studying an eco-friendly sheet, confirming that a planar eco-friendly sheet can be produced by including a transparent layer obtained by processing a crosslinked modified PLA resin composition.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.

In the drawings, the thickness is enlarged to clearly represent the layers and regions. In the drawings, for the convenience of explanation, the thicknesses of some layers and regions are exaggerated.

Hereinafter, formation of an arbitrary structure in the "upper (or lower)" of the description means not only that an arbitrary structure is formed in contact with the upper surface (or lower surface) of the substrate, It is to be understood that the invention is not to be limited to the specific embodiments thereof.

1 is a schematic cross-sectional view of an environmentally friendly sheet according to an embodiment of the present invention.

As shown in FIG. 1, an eco-friendly sheet according to an embodiment of the present invention includes a substrate layer 110; A printing layer 120 formed on the base layer 110; And a transparent layer 130 formed on the printing layer 120.

The substrate layer (110)

The base layer 110 is the most basic layer of the sheet and supports the print layer 120 and the transparent layer 130 formed on the upper part and absorbs the impact of the upper part and the lower part.

The base layer 110 may be a PVC resin sheet, and the PVC resin sheet is excellent in flexibility.

The base layer 110 is preferably formed to a thickness of 0.05 to 3.0 mm, but is not limited thereto. At this time, when the thickness of the base layer 110 is 0.05 mm or less, the supporting and absorbing functions can not be performed properly. When the thickness exceeds 3.0 mm, curing occurs in the upward direction. It causes.

Printing layer (120)

The printing layer 120 is formed on the upper side of the base layer 110 and is formed on the upper surface of the printing layer 120 by a method such as transfer printing, gravure printing, screen printing, offset printing, rotary printing or flexo printing, And forms a pattern in various ways, thereby providing the aesthetics of the sheet.

The printed layer 120 may also be a PVC resin sheet, which is excellent in flexibility.

The printing layer 120 is preferably formed to a thickness of 0.1 to 0.5 mm, but is not limited thereto. If the thickness of the printing layer 120 is less than 0.1 mm, printing may be difficult. If the thickness exceeds 0.5 mm, curing may occur in the upper direction, resulting in an increase in sheet manufacturing cost do.

Transparent layer (130)

The transparent layer 130 is formed on the print layer 120 to give a sense of volume and to protect the pattern formed on the upper surface of the print layer 120.

The transparent layer 130 is characterized in that the crosslinked modified PLA resin composition is processed.

The crosslinked modified PLA resin composition is modified through a crosslinking reaction at the time of opening, and may include a PLA resin, a thermal initiator, and a crosslinking monomer. Specifically, the crosslinked modified PLA resin composition may include 0.1 to 10 parts by weight of a thermal initiator and 0.1 to 10 parts by weight of a crosslinking monomer, based on 100 parts by weight of the PLA resin.

In addition, the crosslinked modified PLA resin composition may further include at least one of a nonphthalate plasticizer, a lubricant, calcium carbonate, and titanium dioxide. Specifically, the crosslinked modified PLA resin composition may contain 5 to 100 parts by weight of a nonphthalate plasticizer, 0.1 to 10 parts by weight of a lubricant, 5 to 1000 parts by weight of calcium carbonate, and 0.5 to 50 parts by weight of titanium dioxide, based on 100 parts by weight of the PLA resin One or more of the moieties.

At this time, the PLA (polylactic acid) resin is a thermoplastic polyester of lactide or lactic acid as a main material of the biodegradable resin, and can be produced by polymerizing lactic acid produced by fermenting starch extracted from corn, potato or the like have. Since the corn, potatoes and the like are a renewable plant resource, the PLA resin that can be obtained from them can effectively cope with problems caused by depletion of petroleum resources.

In addition, the PLA resin is environmentally friendly in that the emission of environmentally harmful substances such as CO ₂ is much lower than that of petroleum-based materials such as polyvinyl chloride (PVC) during use or disposal, .

The PLA resin can be divided into a crystalline PLA (c-PLA) resin and an amorphous PLA (a-PLA) resin. At this time, in the case of the crystalline PLA resin, it is preferable to use an amorphous PLA resin since bleeding may occur in which the plasticizer flows out to the sheet surface. When an amorphous PLA resin is used, there is an advantage that a compatibilizer which is essentially added to prevent the bleeding phenomenon is not added. When an amorphous PLA resin is used, it is most preferable to use a 100% amorphous PLA resin as the PLA resin, and if necessary, a PLA resin in which crystalline and amorphous coexist can be used.

In addition, the crosslinked modified PLA resin composition may include a thermal initiator in order to cause the PLA resin to undergo a crosslinking reaction by heat. The thermal initiator is preferably a radical initiator which is decomposed by heat generated during processing such as plywood processing to form radicals. Specific examples include benzoyl peroxide, dialkyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, dicumene hydroperoxide, t-butylperoxy-2-ethylhexanoate, But are not limited to, at least one selected from the group consisting of azobisdimethylvaleronitrile and azobisisobutyronitrile.

The content of the thermal initiator is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the PLA resin, but is not limited thereto. When the content of the thermal initiator is less than 0.1 parts by weight, the radical initiating reaction hardly occurs. When the amount of the thermal initiator is more than 10 parts by weight, the PLA resin may be deteriorated by the unreacted initiator.

In addition, the crosslinked modified PLA resin composition may include a crosslinking monomer that acts as a crosslinking agent formed between molecular chains of the PLA resin by a crosslinking reaction.

The crosslinking monomer preferably has excellent properties in physical properties such as melt strength, transparency, UV stability, water resistance and solvent resistance when polymerized, and is preferably easily polymerized by heat. Specifically, it is preferably at least one selected from acrylate-based monomers and methacrylate-based monomers having a monofunctional or polyfunctional group, but is not limited thereto.

The content of the crosslinking monomer is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the PLA resin, but is not limited thereto. If the content of the crosslinking monomer is less than 0.1 part by weight, the effect of improving the physical properties such as the melt strength is insufficient. If the content of the crosslinking monomer exceeds 10 parts by weight, compatibility with other materials constituting each layer The overall physical properties of each layer may be deteriorated.

In addition, the crosslinked modified PLA resin composition may further include a plasticizer for processing into a sheet form by a car rendering method.

The plasticizer is preferably a non-phthalate-based plasticizer as an environmentally friendly plasticizer. The plasticizer softens the PLA resin to increase thermoplasticity to facilitate molding at high temperatures. It is preferable to use at least one selected from the group consisting of ATBC (acetyl tributyl citrate) and TBC (Tributyl citrate) as the nonphthalate plasticizer, but the present invention is not limited thereto.

The amount of the nonphthalate plasticizer is preferably 5 to 50 parts by weight per 100 parts by weight of the PLA resin, but is not limited thereto. When the content of the nonphthalate plasticizer is less than 5 parts by weight, the hardness of the PLA resin is increased and the workability may be lowered. When the content of the nonphthalate plasticizer is more than 50 parts by weight, plasticity and flexibility are improved. The physical properties due to the lowered compatibility with the component may be deteriorated.

The crosslinked modified PLA resin composition may further contain calcium carbonate (CaCO ₃ ) as a lubricant or an inorganic filler for reinforcing, and titanium dioxide (TiO ₂ ) as a white pigment for imparting esthetics.

The lubricant is added to prevent the resin from adhering to the calender roll or the press during processing such as car-rendering and extrusion of the biodegradable resin. There are various kinds of these lubricants, but in the present invention, eco-friendly higher fatty acids are used as lubricants, and for example, stearic acid, which is a saturated higher fatty acid having 18 carbon atoms, can be used.

The lubricant is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the PLA resin, but is not limited thereto. If the content of the lubricant is less than 0.1 parts by weight, the effect of using the lubricant can not be obtained. If the content of the lubricant exceeds 10 parts by weight, the impact resistance, heat resistance, gloss and the like of the PLA resin may be deteriorated.

The calcium carbonate is preferably 5 to 1000 parts by weight per 100 parts by weight of the PLA resin, but is not limited thereto. The titanium dioxide is preferably 0.5 to 50 parts by weight per 100 parts by weight of the PLA resin, but is not limited thereto. At this time, when calcium carbonate or titanium dioxide is used in excess of the above range, the bonding force of the other components may be lowered and the workability may be lowered.

The transparent layer may be obtained by processing a crosslinked modified PLA resin composition by a car rendering method. Specifically, the above-described raw materials are mixed and kneaded to prepare a crosslinked modified PLA resin composition, and then processed through a process of car-rendering molding into a desired sheet shape.

The mixing and kneading of the respective raw materials can be performed, for example, by using a liquid mix or a powdery raw material in a super mixer, an extruder, a kneader, a double or triple roll, or the like. For more efficient mixing, the blended raw materials are kneaded at a temperature of about 120 to 200 DEG C using a Banbury mixer or the like, and the kneaded raw materials are kneaded at a temperature of about 120 to 200 DEG C using a two-roll mill or the like And the mixing and kneading steps may be repeatedly performed in multiple stages as in the first and second mixing methods. The car-rendering molding method is also not particularly limited, and can be manufactured by using a conventional apparatus such as an inverted L-type four-roll calender.

The processing conditions of the car rendering system can be appropriately selected in consideration of the composition of the crosslinked modified PLA resin composition to be used and the car rendering processing is performed within a processing temperature range of about 120 to 160 ° C .

The transparent layer 130 is preferably formed to a thickness of 0.1-1.0 mm, but is not limited thereto. At this time, when the transparent layer 130 is formed to a thickness of less than 0.1 mm, the pattern formed on the print layer can not be effectively protected and the volume feeling is lowered. On the other hand, if the thickness of the transparent layer 130 exceeds 1.0 mm, curing may occur in the upper direction, which may cause an increase in sheet production cost.

2 is a schematic cross-sectional view of an environmentally friendly sheet according to another embodiment of the present invention.

As shown in FIG. 2, the environmentally friendly sheet according to another embodiment of the present invention includes an adhesive layer 150; A base layer 110 formed on the adhesive layer 150; A printing layer 120 formed on the base layer 110; A transparent layer 130 formed on the printing layer 120; And a surface treatment layer (140) formed on the transparent layer (130).

1 except for the surface treatment layer 140 and the adhesive layer 150. The description of the base layer 110, the print layer 120, and the transparent layer 130 will be omitted .

Adhesive layer (150)

The adhesive layer 120 may be formed under the base layer 110.

The adhesive layer 120 is preferably an epoxy resin, a polyurethane resin, a polyisocyanate resin, a polyester resin, an acrylate resin, an ethylene-vinyl acetate copolymer resin, a polyamide resin, Based resin, a melamine-based resin, a synthetic rubber-based resin, and a polyvinyl alcohol-based resin, and more preferably a melamine resin, a urethane acrylate resin, a polyurethane resin, or the like.

Surface treatment layer (140)

The surface treatment layer 140 may be formed on the transparent layer 130.

The surface treatment layer 140 is formed to improve the surface quality such as scratch resistance and abrasion resistance of the environmentally friendly sheet and to improve the stain resistance to facilitate cleaning. The surface treatment layer 140 is formed of a polyurethane resin , Urethane acrylate resin, wax, and the like.

For example, when a urethane acrylate resin is used, the urethane acrylate-based UV curable composition may be applied on the transparent layer 130, and cured through ultraviolet irradiation. . Further, a thermosetting wax may be applied on the transparent layer 130, and the resulting mixture may be cured by passing through a hot air oven.

The surface treatment layer 140 is preferably formed to a thickness of 0.01 to 0.1 mm, but is not limited thereto. At this time, when the surface treatment layer 140 is formed to a thickness of less than 0.01 mm, it is difficult to expect an effect of improving physical properties such as scratch resistance. On the other hand, when the surface treatment layer 140 is more than 0.1 mm, there is a problem that an excessive manufacturing cost is required for forming the surface treatment layer and the appearance characteristics of the environmentally friendly sheet may be deteriorated.

The present invention also relates to a method for producing a crosslinked modified PLA resin composition, which comprises: preparing a transparent layer by processing a crosslinked modified PLA resin composition; And laminating the base layer, the print layer formed on the base layer, and the transparent layer formed on the print layer.

The laminate has a thickness of 120 to 160? Temperature conditions. At this time, the laminate is 120 ~ 160? Temperature condition, the transparent layer obtained by processing the crosslinked modified PLA resin composition can maintain excellent heat resistance even under the laminate temperature condition.

In the case of laminating the PVC resin sheet and the PLA resin sheet, severe curling occurs on the PLA resin sheet having a strong modulus compared to the PVC resin sheet, so that there is a problem that an eco-friendly sheet in a flat form can not be produced.

The crosslinked modified PLA resin composition was processed to produce a transparent layer having improved flexibility and heat resistance. The environmentally friendly sheet according to the present invention was produced by laminating a PVC resin sheet and a transparent layer obtained by processing a crosslinked modified PLA resin composition, And the transparent layer obtained by processing the crosslinked modified PLA resin composition have an equivalent level of modulus, the curling is prevented, thereby making it possible to produce an eco-friendly sheet in a flat shape.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the following examples.

[ Example ]

Example

20 g of ATBC (Acetyl Tributyl Citrate, Aekyung Chemical Co., Ltd.) as a non-phthalate plasticizer, 2 g of a methacrylate monomer as a crosslinking monomer, 100 g of a dialkyl peroxide ) And 3 g of stearic acid as a lubricant for preventing sticking in a calender roll with a Banbury mixer were kneaded in a Banbury mixer until the temperature reached 160 ° C, To prepare a crosslinked modified PLA resin composition. Thereafter, the mixture was sufficiently mixed before the calender roll was put in a 120 ° C warming roll for smooth seating in the calender roll, and then the crosslinked modified PLA resin composition passed through the strainer was removed at 140 to 150 ° C , And a transparent layer having a thickness of 0.5 mm was produced.

A printing layer made of a 0.3 mm thick PVC resin sheet formed on the top of the base layer, and a transparent layer formed on the printing layer were formed on a heating drum having a processing temperature of 140 DEG C The laminate was laminated using the embossing machine provided. Thereafter, a polyurethane adhesive layer was formed on the lower part of the substrate layer, a urethane acrylate UV curable paint was applied to the upper part of the prepared transparent layer, and a surface treatment layer having a thickness of 0.05 mm was formed by irradiating ultraviolet rays, Were prepared.

Comparative Example

In the PLA resin composition of the present example, except for the dialkyl peroxide, which is a thermal initiator, and the methacrylate monomer as a crosslinking monomer, instead of the calendering, a film having a thickness of 0.5 mm Was prepared in the same manner as in Example 1, except that a transparent layer having a thickness of 100 nm was produced.

Experimental Example

In order to evaluate the physical properties of the environmentally friendly sheet prepared according to Examples and Comparative Examples, the lamination processability was evaluated under a heating drum condition having a surface temperature of 120 to 160 DEG C, and the lamination processability was evaluated from 1 point (very low) to 5 points (very high) And the heat resistance was evaluated relatively. The results are shown in Table 1 below.

division Stackability Heat resistance Example Excellent in lamination processability 5 points Comparative Example Adheres to the surface of the heating drum and poor lamination processability 2 points

As shown in Table 1, it was found that the laminate processability and flexibility were significantly superior to the comparative examples by including the transparent layer obtained by processing the crosslinked modified PLA resin composition in the examples.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

110: substrate layer
120: Printed layer
130: transparent layer
140: Surface treatment layer
150: Adhesive layer

Claims

A base layer;
A printing layer formed on the base layer; And
And a transparent layer formed on the print layer,
Wherein the transparent layer is obtained by processing a crosslinked modified PLA resin composition
Eco-friendly sheet.

The method according to claim 1,
Wherein the base layer or the printing layer is a PVC resin sheet
Eco-friendly sheet.

The method according to claim 1,
Wherein the crosslinked modified PLA resin composition comprises a PLA resin, a thermal initiator and a crosslinking monomer, and is modified through a crosslinking reaction at the time of opening
Eco-friendly sheet.

The method of claim 3,
Wherein the crosslinked modified PLA resin composition comprises 0.1 to 10 parts by weight of a thermal initiator and 0.1 to 10 parts by weight of a crosslinking monomer based on 100 parts by weight of the PLA resin
Eco-friendly sheet.

The method of claim 3,
Wherein the crosslinked modified PLA resin composition further comprises at least one selected from the group consisting of a nonphthalate plasticizer, a lubricant, calcium carbonate, and titanium dioxide
Eco-friendly sheet.

The method of claim 3,
The crosslinked modified PLA resin composition comprises 5 to 100 parts by weight of a nonphthalate plasticizer, 0.1 to 10 parts by weight of a lubricant, 5 to 1000 parts by weight of calcium carbonate, and 0.5 to 50 parts by weight of titanium dioxide, based on 100 parts by weight of the PLA resin &Lt; RTI ID = 0.0 >
Eco-friendly sheet.

The method according to claim 1,
The base layer is formed to a thickness of 0.05 to 3.0 mm
Eco-friendly sheet.

The method according to claim 1,
The printing layer is formed to a thickness of 0.1 to 0.5 mm
Eco-friendly sheet.

The method according to claim 1,
Wherein the transparent layer is obtained by processing a crosslinked modified PLA resin composition by a car rendering method
Eco-friendly sheet.

The method according to claim 1,
The transparent layer is formed to have a thickness of 0.1 to 1.0 mm
Eco-friendly sheet.

The method according to claim 1,
A surface treatment layer is further formed on the transparent layer
Eco-friendly sheet.

12. The method of claim 11,
The surface treatment layer is formed to a thickness of 0.01 to 0.1 mm
Eco-friendly sheet.

The method according to claim 1,
An adhesive layer is further formed on the bottom of the base layer
Eco-friendly sheet.

Processing the crosslinked modified PLA resin composition to produce a transparent layer; And
Comprising the steps of: laminating a substrate layer, a print layer formed on the substrate layer and the transparent layer formed on the print layer,
A method of manufacturing an environmentally friendly sheet.

15. The method of claim 14,
The laminate is then subjected to a temperature of 120 to 160 캜
A method of manufacturing an environmentally friendly sheet.